CN110229163B

CN110229163B - Method for synthesizing hydroxyalkyl triethylene diamine compound

Info

Publication number: CN110229163B
Application number: CN201910473696.2A
Authority: CN
Inventors: 王晓林; 杨玉淳; 李会; 崔余存
Original assignee: Jiaxing Runbo Chemical Technology Co ltd
Current assignee: Jiaxing Runbo Chemical Technology Co ltd
Priority date: 2019-06-01
Filing date: 2019-06-01
Publication date: 2022-05-24
Anticipated expiration: 2039-06-01
Also published as: CN110229163A

Abstract

A method for synthesizing a hydroxyalkyl triethylene diamine compound comprises the steps of taking solid Phosphorylated Graphene (PGO) as a catalyst, adding any one of a mono-substituted dihydroxyalkyl piperazine derivative and a polar solvent with a dielectric constant larger than 10 into a reaction kettle, heating to 100-300 ℃ under the atmosphere of nitrogen, keeping the pressure of the reaction kettle at 1-10 MPa, stirring for reaction for 1-5 hours, cooling to 30-60 ℃, then centrifugally separating the catalyst and a reaction solution, and carrying out reduced pressure rectification on the reaction solution to obtain the hydroxyalkyl triethylene diamine compound shown in the formula (I). The invention has simple process and the catalyst can be recycled. In the synthesis process of the 2-hydroxymethyl triethylene diamine, the conversion rate of the reactant dihydroxyalkyl piperazine can reach more than 95%, and the selectivity of the product 2-hydroxymethyl triethylene diamine can reach more than 90%.

Description

Method for synthesizing hydroxyalkyl triethylene diamine compound

Technical Field

The present invention belongs to the field of synthetic chemical engineering technology. In particular to a method for synthesizing hydroxyalkyl triethylene diamine compounds.

Background

The 2-hydroxymethyl triethylene diamine is a novel polyurethane foaming amine catalyst, is a solid cyclic tertiary amine containing hydroxyl, and participates in reaction during polyurethane foam production compared with triethylene diamine, and hardly generates volatile components and odor. Patent CN104557947A provides a method for producing 2-hydroxymethyl triethylene diamine by a fixed bed, but the method is relatively complex in process and only aims at the synthesis of hydroxymethyl triethylene diamine; patents CN102046629A, CN103270039A provide a method for producing hydroxyalkyltriethylenediamine compounds, which uses metal phosphate, organic phosphorus, etc. as a catalyst, does not involve the use of a catalyst, and is not high in atom economy. And none of the above patents mention the use of Phosphorylated Graphene (PGO) as a catalyst which can be recycled.

Disclosure of Invention

The invention aims to provide a novel process method for preparing the hydroxyalkyl triethylene diamine compound in an environment-friendly, environment-friendly and efficient green way, wherein a catalytic system has no pollution to the environment, and a catalyst is repeatedly utilized.

The technical scheme of the invention is as follows: the invention relates to a method for synthesizing a hydroxyalkyl triethylene diamine compound,

(Ⅰ)

the preparation method is characterized in that solid Phosphorylated Graphene (PGO) is used as a catalyst, one of a mono-substituted dihydroxyalkyl piperazine derivative and a polar solvent with a dielectric constant larger than 10 is added into a reaction kettle, the temperature is raised to 100-300 ℃ under the nitrogen atmosphere, the pressure of the reaction kettle is 1-10 MPa, the reaction is stirred for 1-5 hours, the temperature is reduced to 30-60 ℃, then the catalyst and a reaction liquid are centrifugally separated, and the reaction liquid is subjected to reduced pressure rectification to obtain the hydroxyalkyl triethylenediamine compound shown in the formula (I).

The solid Phosphorylated Graphene (PGO) catalyst is a highly phosphorylated graphene material, a phosphate group on the surface of graphene is a reaction active site, and the content of phosphate groups on the Phosphorylated Graphene (PGO) catalyst is 10-90%.

The mass ratio of the mono-substituted dihydroxyalkyl piperazine derivative to the catalyst is 5.0-50.0, preferably 10-30.

The mono-substituted dihydroxyalkyl piperazine derivative is

(Ⅱa) (Ⅱb)

In the above formulae (IIa) and (IIb), R and n are as defined in the above formula (I).

The monosubstituted dihydroxyalkyl piperazine derivative is one or more of 1- (2 ', 3' -dihydroxypropyl) piperazine, 1- (1 '-hydroxymethyl-2' -hydroxyethyl) piperazine, 1- (2 ', 4' -dihydroxybutyl) piperazine, 1- (1 '-hydroxymethyl-3' -hydroxypropyl) piperazine and the like.

The solvent is any one of polar solvents with a dielectric constant larger than 10, and the mass ratio of the mono-substituted dihydroxyalkyl piperazine derivative to the solvent is 0.2-1.

The reaction temperature is 100 to 300 ℃, preferably 150 to 250 ℃.

The reaction pressure is 1 to 10MPa, preferably 2 to 5 MPa.

The Phosphorylated Graphene (PGO) catalyst is deactivated after being used for many times, can be repeatedly washed by ethanol, acetone and water, and is dried in vacuum, so that the regenerated catalyst can be repeatedly used.

The invention takes highly phosphorylated graphene as a catalyst, and the catalyst has the following beneficial effects: the catalyst has simple preparation method, good compatibility with a reaction system, simple and thorough separation of the catalyst and the reaction system after the reaction is finished, and no obvious inactivation of the catalyst is observed after the catalyst is continuously used for 5 times. The invention has simple process and the catalyst can be recycled. In the synthesis process of the 2-hydroxymethyl triethylene diamine, the conversion rate of a reactant dihydroxyalkyl piperazine can reach more than 95%, and the selectivity of a product 2-hydroxymethyl triethylene diamine can reach more than 90%.

Detailed Description

The following examples illustrate the invention by way of example of the synthesis of 2-hydroxymethyltriethylenediamine, without limiting the scope of the description. The chemical reagents used in the following synthesis examples are commercially available, and the preparation of Phosphorylated Graphene (PGO) and Gd pairs thereof were carried out according to the article "Yangxieyi et al³⁺The adsorption performance research of (1) is carried out by a co-production method.

The first embodiment is as follows:

the method comprises the steps of adopting a 5L high-pressure reaction kettle, diluting 1 kg of 1- (2 ', 3' -dihydroxypropyl) piperazine with methanol until the concentration is 50% of the original concentration, adding the diluted 1- (2 ', 3' -dihydroxypropyl) piperazine into the high-pressure reaction kettle, weighing 50g of PGO prepared by a reference method, adding the PGO into the reaction kettle, replacing the nitrogen for 3 times at 0.5 MPa, keeping the nitrogen at normal pressure, setting the temperature to be 165 ℃, finally controlling the temperature to be 170 ℃, reacting for 4 hours at the pressure of about 2.5 MPa, cooling to the normal temperature, releasing pressure and discharging, centrifugally recovering a PGO catalyst from a reaction solution, detecting the conversion rate by using a gas chromatography to be 97%, and obtaining the selectivity of the 2-hydroxymethyl triethylenediamine product to be 94%. The methanol is recovered by atmospheric distillation and rectified under reduced pressure to obtain 728 g of 2-hydroxymethyl triethylene diamine with the purity of 99 percent.

Example two:

the method comprises the steps of adopting a 5L high-pressure reaction kettle, diluting 1 kg of 1- (2 ', 3' -dihydroxypropyl) piperazine with methanol until the concentration is 50% of the original concentration, adding the diluted 1- (2 ', 3' -dihydroxypropyl) piperazine into the high-pressure reaction kettle, finally adding 47g of PGO recovered in the first embodiment into the reaction kettle, performing nitrogen replacement for 3 times at 0.5 MPa, finally maintaining normal-pressure nitrogen, setting the temperature to be 165 ℃, finally controlling the temperature to be 170 ℃, reacting for 4 hours at the pressure of about 2.5 MPa, cooling to the normal temperature, releasing pressure and discharging, centrifugally recovering a PGO catalyst from a reaction solution, detecting the conversion rate by using a gas chromatography to be 95%, and obtaining the selectivity of 2-hydroxymethyl triethylenediamine of 95%. The methanol is recovered by atmospheric distillation and rectified under reduced pressure to obtain about 720 g of 2-hydroxymethyl triethylene diamine with the purity of 99 percent.

Example three:

the method comprises the steps of adopting a 5L high-pressure reaction kettle, diluting 1 kg of 1- (1 '-hydroxymethyl-2' -hydroxyethyl) piperazine with methanol until the concentration is 50% of the original concentration, adding the diluted 1- (1 '-hydroxymethyl-2' -hydroxyethyl) piperazine into the high-pressure reaction kettle, finally weighing 50g of PGO prepared by a reference method, adding the PGO into the reaction kettle, performing nitrogen replacement for 3 times under 0.5 MPa, finally keeping the nitrogen under normal pressure, setting the temperature to be 175 ℃, finally controlling the temperature to be 180 ℃, reacting for 4 hours under the pressure of about 3.5 MPa when the temperature reaches 180 ℃, cooling to the normal temperature, releasing pressure and discharging, centrifugally recovering a PGO catalyst from a reaction solution, detecting the conversion rate by using a gas chromatography to be 95%, and obtaining the selectivity of 2-hydroxymethyl triethylenediamine of 91%. The methanol is recovered by atmospheric distillation and rectified under reduced pressure to obtain about 690 g of 2-hydroxymethyltriethylenediamine with the purity of 99 percent.

Example four:

the method comprises the steps of adopting a 5L high-pressure reaction kettle, diluting 1 kg of 1- (1 '-hydroxymethyl-2' -hydroxyethyl) piperazine with methanol until the concentration is 50% of the original concentration, adding the diluted 1- (1 '-hydroxymethyl-2' -hydroxyethyl) piperazine into the high-pressure reaction kettle, finally adding 46g of PGO recovered in the third embodiment into the reaction kettle, replacing the nitrogen with 0.5 MPa for 3 times, finally keeping the nitrogen at normal pressure, setting the temperature to be 175 ℃, finally controlling the temperature to be 180 ℃, enabling the pressure to be about 3.5 MPa, enabling the temperature to reach 180 ℃, reacting for 4 hours, cooling to the normal temperature, relieving pressure and discharging, centrifugally recovering a PGO catalyst from a reaction solution, detecting the conversion rate by using a gas chromatography, and enabling the selectivity of a product 2-hydroxymethyl triethylenediamine to be 92%. The methanol is recovered by atmospheric distillation and rectified under reduced pressure to obtain about 690 g of 2-hydroxymethyltriethylenediamine with the purity of 99 percent.

Claims

1. A method for synthesizing a hydroxyalkyl triethylene diamine compound (I) comprises the following steps:

(Ⅰ)

wherein R is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms; n =0,1,2,3 is an integer, and is characterized in that solid Phosphorylated Graphene (PGO) is used as a catalyst, a mono-substituted dihydroxy alkyl piperazine derivative and a polar solvent with a dielectric constant greater than 10 are added into a reaction kettle, the mixture is heated to 100-300 ℃ under a nitrogen atmosphere, the pressure of the reaction kettle is 1-10 MPa, the mixture is stirred and reacted for 1-5 hours, the temperature is reduced to 30-60 ℃, then the catalyst and a reaction solution are centrifugally separated, the reaction solution is subjected to reduced pressure rectification to obtain a hydroxyalkyl triethylenediamine compound of the formula (I), the polar solvent with the dielectric constant greater than 10 is methanol, the solid Phosphorylated Graphene (PGO) catalyst is a highly phosphorylated graphene material, a phosphate group on the surface of the graphene is a reaction active site, and the phosphate content on the Phosphorylated Graphene (PGO) catalyst is 10-90%.

2. The method for synthesizing hydroxyalkyltriethylenediamine compound (I) according to claim 1, wherein the mono-substituted dihydroxyalkyl piperazine derivative is one or more of 1- (2 ', 3' -dihydroxypropyl) piperazine, 1- (1 '-hydroxymethyl-2' -hydroxyethyl) piperazine, 1- (2 ', 4' -dihydroxybutyl) piperazine, and 1- (1 '-hydroxymethyl-3' -hydroxypropyl) piperazine.

3. The method for synthesizing hydroxyalkyltriethylenediamine compound (I) according to claim 1, wherein the mass ratio of the mono-substituted dihydroxyalkyl piperazine derivative to the catalyst is 5.0-50.0.

4. The method for synthesizing hydroxyalkyltriethylenediamine compound (I) according to claim 1, wherein the mass ratio of the mono-substituted dihydroxyalkyl piperazine derivative to the solvent is 0.2-1.

5. The method for synthesizing hydroxyalkyltriethylenediamine compound (I) according to claim 1, wherein the reaction temperature is 100 to 300 ℃.

6. The method for synthesizing hydroxyalkyltriethylenediamine compound (1) according to claim 1, wherein the reaction pressure is 1 to 10 MPa.